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Fine Control of the Redox Reactivity of a Nonheme Iron( III)-Peroxo Complex by Binding Redox-Inactive Metal Ions

Title
Fine Control of the Redox Reactivity of a Nonheme Iron( III)-Peroxo Complex by Binding Redox-Inactive Metal Ions
Authors
Bae, Seong HeeLee, Yong-MinFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2017
Journal Title
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
ISSN
1433-7851JCR Link1521-3773JCR Link
Citation
vol. 56, no. 3, pp. 801 - 805
Keywords
iron-peroxo intermediatesLewis aciditynonheme iron enzymesreactive speciesredox-inactive metal ions
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Redox-inactive metal ions are one of the most important co-factors involved in dioxygen activation and formation reactions by metalloenzymes. In this study, we have shown that the logarithm of the rate constants of electron-transfer and C-H bond activation reactions by nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)Fe-III(O-2)](+)-Mn+ (Mn+=Sc3+, Y3+, Lu3+, and La3+), increases linearly with the increase of the Lewis acidity of the redox-inactive metal ions (Delta E), which is determined from the g(zz) values of EPR spectra of O-2(center dot-)-Mn+ complexes. In contrast, the logarithm of the rate constants of the [(TMC)Fe-III(O-2)](+)-Mn+ complexes in nucleophilic reactions with aldehydes decreases linearly as the Delta E value increases. Thus, the Lewis acidity of the redox-inactive metal ions bound to the mononuclear nonheme iron(III)-peroxo complex modulates the reactivity of the [(TMC)Fe-III(O-2)](+)-Mn+ complexes in electron-transfer, electrophilic, and nucleophilic reactions.
DOI
10.1002/anie.201610828
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자연과학대학 > 화학·나노과학전공 > Journal papers
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